CN115190905A - High creep recovery, low modulus polymer systems and methods of making the same - Google Patents
High creep recovery, low modulus polymer systems and methods of making the same Download PDFInfo
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- CN115190905A CN115190905A CN202180017469.4A CN202180017469A CN115190905A CN 115190905 A CN115190905 A CN 115190905A CN 202180017469 A CN202180017469 A CN 202180017469A CN 115190905 A CN115190905 A CN 115190905A
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 24
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6245—Polymers having terminal groups containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Abstract
Disclosed herein is a method of making an adhesive composition, the method comprising: providing a urethane acrylate, combining it with a vinyl ether, and co-curing the combination to form an adhesive composition, wherein the adhesive composition after curing has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃. The resulting adhesive composition is also disclosed.
Description
Background
Electronic devices that display images, such as smart phones, digital cameras, notebook computers, navigation units, and televisions, include a display panel for displaying images. Thin and light flat display panels are widely used for image display. There are many types of flat display panels including Liquid Crystal Display (LCD) panels, organic Light Emitting Diode (OLED) display panels, plasma Display Panels (PDPs), electrophoretic display (EPD) panels, and the like.
Flexible electronic displays or foldable displays are being developed that can be folded to provide portability and unfolded to increase viewing area. Flexible electronic displays, wherein the display can be freely bent without cracking or breaking, are a rapidly emerging field of technology for manufacturing electronic devices using, for example, flexible plastic substrates.
With the advent of these flexible electronic displays, there is an increasing demand for adhesives, particularly Optically Clear Adhesives (OCAs), for use as an assembly layer or gap-fill layer between the outer cover lens or sheet (based on glass, PET, PC, PMMA, polyimide, PEN, cyclic olefin copolymer, etc.) and the underlying display module of an electronic display assembly. The presence of the OCA improves the performance of the display by increasing brightness and contrast while also providing structural support for the assembly. In a flexible assembly, the OCA will also serve as an assembly layer that, in addition to the typical OCA function, can absorb most of the fold-induced stress to prevent damage to the fragile elements of the display panel and protect the electronic components from breaking under the stress of folding. The OCA layer may also be used to position and maintain the neutral bending axis at or at least in the vicinity of fragile elements of the display, such as barrier layers, drive electrodes or thin film transistors of an Organic Light Emitting Display (OLED).
Typical OCAs are viscoelastic in nature, intended to provide durability under a range of environmental exposure conditions and high frequency loads. In this case, a high level of adhesion and some balance of viscoelastic properties are maintained to achieve good pressure sensitive behavior and to incorporate damping properties in the OCA. However, these characteristics are not sufficient enough to enable a foldable or durable display.
Foldable displays for OLED devices require highly flexible optical adhesives to bond the plastic substrates together. Normal folding tests require the adhesive to pass through 100,000 cycles of 1mm radius (180 degree bend) folds over the entire temperature range of-20 ℃ to 85 ℃. There were no commercial products meeting this test. The foldable adhesive should have a high recovery rate and low residual strain to achieve good foldability.
Two important properties of OCAs for use in foldable display devices are modulus and creep recovery. When the device is folded, the folding creates shear stress between the adhesive and the substrate at the ends of the device, while creating compression in the bending region at the middle of the device. When the device returns to a flat state, the stress in these areas is relieved.
In particular for adhesives used in foldable displays, it is highly desirable to have polymer systems that exhibit very low modulus (especially at low temperatures) and high creep recovery. These two physical properties are usually contradictory. Polymeric structures exhibiting high creep recovery (creep recovery) generally have high modulus, while polymeric structures exhibiting low modulus have low creep recovery. For example, known high creep recovery polymers require highly crosslinked networks with high elasticity, which typically have relatively high modulus, especially at low temperatures.
Thus, there remains a need for polymers that exhibit a combination of low modulus and high creep recovery.
Disclosure of Invention
Disclosed herein is a novel co-cured polyacrylate/vinyl ether adhesive polymer that exhibits very low modulus (less than 10.0 mPa) at-20 ℃ and excellent creep recovery (greater than 50%). The adhesive polymer composition achieves a combination of low modulus with high creep recovery, in particular a combination of creep recovery of >70% to >90% with a modulus at-20 ℃ of <1.0mPa to <0.3 mPa.
Also disclosed herein is a method of making an adhesive composition, the method comprising: co-curing a urethane acrylate and a vinyl ether to form the adhesive composition, wherein the adhesive composition after curing has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃.
Detailed Description
Disclosed herein is a novel co-cured polyacrylate/vinyl ether adhesive polymer composition that exhibits very low modulus (less than 10.0 mPa) at-20 ℃ and excellent creep recovery (greater than 50%). The polymer composition prepared by this method achieves a combination of low modulus with high creep recovery, in particular a combination of creep recovery of >70% to >90% with a modulus of <1.0mPa to <0.3mPa at-20 ℃.
Also disclosed herein is a method of making an adhesive composition, the method comprising: co-curing a urethane acrylate and a vinyl ether resin to form the adhesive composition, wherein the adhesive composition after curing has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃. The polymer composition achieves a combination of low modulus with high creep recovery, in particular a combination of a creep recovery of >70% to >90% with a modulus of <1.0mPa to <0.3mPa at-20 ℃.
The polyurethane acrylates used herein may be prepared by reacting a multi-branched diol with a diisocyanate to obtain a polyurethane and reacting the polyurethane with an acrylate to form a polyurethane acrylate, as described in more detail below.
The resulting urethane acrylate/vinyl ether adhesive composition exhibits a very low modulus at-20 ℃ and exhibits excellent creep recovery. In particular, creep recovery may be greater than about 70%, such as greater than about 90%; and the modulus at-20 ℃ may be less than about 4.0mPa, such as less than about 1.0mPa, or even less than about 0.3mPa.
In addition to the urethane acrylate and vinyl ether, the adhesive composition may also contain other ingredients.
Suitable urethane acrylates for use in the present invention include the following:
vinyl ethers that may be used in the present invention include the following:
adhesive polymers formed by co-curing urethane acrylates and vinyl ethers surprisingly have a combination of very high creep recovery and very low modulus. Applicants have discovered that the incorporation of vinyl ether monomers into acrylate polymer systems can significantly reduce the modulus and Tg of the resulting polymer while also producing very high creep recovery at very low modulus. This combination of physical properties of very low modulus at low temperatures and very high creep recovery has not previously been demonstrated in polymeric binder systems and is an unexpected beneficial result.
In one embodiment, a method of making an adhesive composition comprises: combining a urethane acrylate and a vinyl ether to form a mixture, and co-curing the mixture to form an adhesive composition, wherein the adhesive composition after curing has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃.
In another embodiment, the urethane acrylate used in the process is produced by: providing a multi-branched diol; reacting the multi-branched diol with a diisocyanate to obtain a polyurethane; and reacting the polyurethane with acrylic groups to form a polyurethane acrylate. The diol may have a molecular weight greater than about 1000 g/mol.
In another embodiment, co-curing is carried out by photo-curing or thermal curing.
In another embodiment, the diisocyanate is an aliphatic diisocyanate.
In another embodiment, the urethane acrylate and vinyl ether are combined in a vinyl ether to urethane acrylate molar ratio of equal to or less than about 1.
In another embodiment, the urethane acrylate has a molecular weight in excess of about 25000 g/mol.
In another embodiment, the adhesive composition has a modulus of less than about 1.0mPa at-20 ℃ and a creep recovery of greater than about 70%.
In another embodiment, the adhesive composition has a modulus of less than about 0.3mPa and a creep recovery of greater than about 90% at-20 ℃.
In another embodiment, the urethane acrylate has a glass transition temperature of less than 10 ℃.
In another embodiment, the polyurethane acrylic polymer has a glass transition temperature of less than-30 ℃.
In another embodiment, the urethane acrylic polymer is combined with a photoinitiator or thermal initiator prior to the co-curing step.
In another embodiment, the vinyl ether can be selected from the group consisting of poly (butyl vinyl ether), poly (ethyl vinyl ether), poly (hexyl vinyl ether), poly (isobutyl vinyl ether), poly (isopropyl vinyl ether), poly (methyl vinyl ether), poly (octyl vinyl ether), poly (propyl vinyl ether), and combinations thereof.
In another embodiment, the urethane acrylate may be selected from the group consisting of poly (2-ethylhexyl acrylate), poly (2, 3, -tetrafluoropropyl acrylate), poly (4-cyanobutyl acrylate), poly (butyl acrylate), poly (dodecyl acrylate), poly (ethyl acrylate), poly (hexyl acrylate), poly (isobutyl acrylate), poly (isopropyl acrylate), poly (nonyl acrylate), poly (propyl acrylate), poly (sec-butyl acrylate), poly (tetrahydrofurfuryl acrylate), poly (decyl methacrylate), poly (dodecyl methacrylate), poly (hexyl methacrylate), poly (isodecyl methacrylate), poly (octyl methacrylate), and combinations thereof.
The present disclosure also provides an adhesive composition comprising: a co-cured mixture of a urethane acrylate and a vinyl ether, wherein the adhesive composition has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃.
In one embodiment, the adhesive composition has a modulus of less than about 1.0mPa at-20 ℃ and a creep recovery of greater than about 70%.
In one embodiment, the adhesive composition has a modulus of less than about 0.3mPa and a creep recovery of greater than about 90% at-20 ℃.
In another embodiment, the molar ratio of vinyl ether to acrylic monomer is less than about 1.
In another embodiment, no solvent is present in the composition.
In another embodiment, the composition further comprises a thermal initiator or a photoinitiator.
In another embodiment, the diols used to prepare the urethane acrylates used in the present invention have a multi-branched polymer backbone, exemplified as follows:
synthesis of urethane acrylate
Polyfarnesene polyurethane Synthesis results
Dimer acid polyurethane Synthesis results
(NBJ 408535) 3000g/mol of a dihydroxylated polyfarnesene (CVX 50452, 40g, 0.0133mol) was added to a 100mL reactor equipped with an overhead stirrer (overhead stirrer) heated to 80 ℃. Isodecyl acrylate (18.8g, 0.0887mol) was added, followed by dibutyltin dilaurate (0.03g, 0.0001mol) and Irganox 1010 (0.03 g). IPDI (3.46g, 0.0156mol) was then added in two portions (95% addition to the first shot). The reaction was monitored by infrared spectroscopy and the persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the addition of the hydroxyl quencher. After stabilization of the isocyanate concentration by infrared spectroscopy, 4-hydroxybutyl acrylate (0.11g, 0.0008 mol) was added. After one hour, butanol (0.06g, 0.0008 mol) was added to terminate the quenching reaction. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =19.9kg/mol, mw =39.9kg/mol,
(NBJ 408536) 3000g/mol of dihydroxylated polyfarnesene (CVX 504)52,100g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. Heptane (133 g) was added, followed by dibutyltin dilaurate (0.07 g). IPDI (8.165) was then added in two portions (93% in the first shot). The reaction was monitored by infrared spectroscopy and the persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the addition of the hydroxyl quencher. After stabilization of the isocyanate concentration was observed by infrared spectroscopy, 4-hydroxybutyl acrylate (0.2 g) and butanol (0.11 g) were added together. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =75.2kg/mol, mw =164.0kg/mol,
(NBJ 408537) 3000g/mol of a dihydroxylated polyfarnesene (CVX50452, 152g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. Isodecyl acrylate (65 g) was added, followed by dibutyltin dilaurate (0.106 g) and Irganox 1010 (0.106 g). IPDI (12.90948 g) was then added in two portions (92% addition to the first shot). The reaction was monitored by infrared spectroscopy and the persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the addition of the hydroxyl quencher. After stabilization of the isocyanate concentration was observed by infrared spectroscopy, 4-hydroxybutyl acrylate (0.617 g) and butanol (0.317 g) were added together. This combination is intended to obtain a difunctional polymer chain of 25: monofunctional Polymer chain: statistical proportion of non-functional polymer chains. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =40.9kg/mol, mw =156.7kg/mol,
(NBJ 408541) 3000g/mol of dihydroxylated polyol (Priplast 3196-Croda,155.5 g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. 2-ethylhexyl acrylate (66.6 g) was added, followed by dibutyltin dilaurate (0.108 g) and Irganox 1010 (0.108 g). IPDI (12.844 g) was then added in two portions (in a first shot)Add 92%). The reaction was monitored by infrared spectroscopy and the persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the addition of the hydroxyl quencher. After stabilization of the isocyanate concentration was observed by infrared spectroscopy, 4-hydroxybutyl acrylate (1.98 g) and butanol (2.04 g) were added together. This combination is intended to obtain a difunctional polymer chain of 10: monofunctional Polymer chain: statistical proportion of non-functional polymer chains. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =8.1kg/mol, mw =85kg/mol,
(NBJ 408544) 3000g/mol of dihydroxylated polyol (Priplast 3196-Croda,305.88 g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. 2-ethylhexyl acrylate (131.1 g) was added, followed by dibutyltin dilaurate (0.214 g) and Irganox 1010 (0.214 g). IPDI (25.69 g) was then added in two portions (92% addition in the first shot). The reaction was monitored by infrared spectroscopy and the persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the addition of the hydroxyl quencher. After stabilization of the isocyanate concentration was observed by infrared spectroscopy, 4-hydroxybutyl acrylate (1.05 g) and butanol (1.08 g) were added together. This combination is intended to obtain a bifunctional polymer chain of 10: monofunctional polymer chain: statistical proportions of non-functional polymer chains. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =30.3kg/mol, mw =580kg/mol,
(NBJ 408546) 3000g/mol of a dihydroxylated polyol (Priplast 3196-Croda,217.76 g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. 2-ethylhexyl acrylate (93.3 g) was added followed by dibutyltin dilaurate (0.152 g) and Irganox 1010 (0.152 g). IPDI (18.29 g) was then added in two portions (92% addition in the first shot). The reaction was monitored by infrared spectroscopy and the hydroxyl groups were addedThe persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the quenching. After stabilization of the isocyanate concentration by infrared spectroscopy, 4-hydroxybutyl acrylate (2.72 g) was added. This combination is intended to obtain a bifunctional polymer chain of 100: monofunctional polymer chain: statistical proportions of non-functional polymer chains. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =22.8kg/mol, mw =111.2kg/mol,
(NBJ 408550) 3000g/mol of dihydroxylated polyol (Priplast 3196-Croda,176.1 g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. 2-ethylhexyl acrylate (75.47 g) was added followed by dibutyltin dilaurate (0.123 g) and Irganox 1010 (0.123 g). IPDI (14.794 g) was then added in two portions (92% addition in the first shot). The reaction was monitored by infrared spectroscopy and the persistence of the isocyanate peak (about 2200 cm-1) was confirmed before the addition of the hydroxyl quencher. After stabilization of the isocyanate concentration was observed by infrared spectroscopy, 1, 4-butanediol vinyl ether (2.72 g) and butanol (0.557) were added together. This combination is intended to obtain a difunctional polymer chain of 25: monofunctional polymer chain: statistical proportions of non-functional polymer chains. Infrared spectroscopy was used to confirm complete conversion of the isocyanate. The synthesis results are as follows: mn =25.5kg/mol, mw =131.3kg/mol,
(NBJ 408553) 5000g/mol of polyfarnesene monoalcohol (CVX50457, 105g) was added to a 1.5L reactor equipped with an overhead stirrer heated to 80 ℃. Dibutyl tin dilaurate (0.073 g) and Irganox 1010 (0.073 g) were added. AOI (3.33 g) was then added in one portion. The reaction was monitored by infrared spectroscopy and the disappearance of the isocyanate peak (about 2200 cm-1) was confirmed to give a fully monofunctional material.
Another set of polymers was designed and synthesized by a similar methodology.
By adjusting the feed ratio of the end capping groups, statistically monofunctional polymers can be prepared, as described below. In the above description, GI-2000IPDIin = 7-10O-butyl 4-HBA-OGI-2000n 4-HBA-OPPGO-butyl mGI-2000n 4-HBA-OPriplastO-butyl mIPDIPDIIPDIIPDIIPDIPDI.
MJ408666GGI2000 blended with PPG with 0.33HBA terminal functionality (functionality).
MJ408657D GI2000 blended with PPG with 0.50HBA terminal functionality.
MJ408650E GI2000 blended with PPG2000 having a 0.50HBA terminal functionality.
MJ408619F GI2000 blended with PPG with 0.33 terminal functionality.
MJ408690F GI2000 with 0.5-hydroxybutyl vinyl ether end-functionality.
MJ408642D GI2000 with 0.5HBA end functionality.
These resins are synthesized by the above procedure using suitable starting materials.
The following abbreviations are used herein: 4-HBA-4-hydroxybenzoic acid; IDA-iminodiacetic acid; IPDI-isophorone diisocyanate; IBA-isobornyl acrylate; AOI;2-BCA; VE-vinyl esters; 2-EHA-2-ethylhexyl acrylate; 2-EH VA; 2-EHVE-2-ethylhexyl vinyl ether; 4-HBVE-4-hydroxybutyl vinyl ether. Irganox 1010 is the trade name of pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Synthesis of 2-decyl-1-tetradecanol acrylate
This acrylate was synthesized by reacting 100.0g (0.281 mol) of 2-decyl-1-tetradecanol with 33.38g (0.369 mol) of acryloyl chloride in toluene using triethylamine as a catalyst. The product was a colorless low viscosity liquid.
Synthesis of high MW polymers
The synthesis of ultra-high MW polyacrylates is carried out by the known SET-LRP synthesis procedure described below:
to a 250ml four necked round bottom flask with mechanical stirrer, condenser, addition funnel (additional funnel) and rubber septum was added acetonitrile (13 g), t-butyl acrylate (12.80g, 100mmol), copper mesh (0.43 g) (treated with 0.1N aqueous hydrochloric acid and rinsed with acetone), copper (II) bromide (0.013g, 0.05mmol, or using a stock solution of CuBr2 in CH3 CN); purging the mixture with nitrogen for 30 minutes, and then heating to the temperature of 45 ℃; the initiator α -bromoisobutyric acid tert-butyl ester (1.115g, 5mmol) and the ligand Me6TREN (0.12g, 0.50mmol, or using a stock solution in CH3 CN) were injected into the above solution by a gas-tight syringe; by using 1 The reaction was monitored by H NMR and GPC until the conversion of tert-butyl acrylate was > 85% (. About.2H).
Following the above procedure but using the appropriate starting materials, the following were prepared.
Synthesis of a terpolymer of methyl acrylate (methacrylate), n-butyl acrylate and t-butyl acrylate (tert-polymer) (NBJ 408529).
The synthesis procedure is described in the following feed ratios:
GPC scans and reaction times are listed below:
synthesis of a terpolymer of 2-ethylhexyl acrylate, n-butyl acrylate and 4-hydroxybutyl acrylate (NBJ 408530).
The synthesis procedure is described in the following feed ratios:
| MW | g | mole of | Molar ratio of | Weight percent | |
| 2-ethylhexyl acrylate | 184.00 | 220.80 | 1.2000 | 2000.0 | 18.70％ |
| Acrylic acid 4-hydroxybutyl ester | 144.00 | 138.24 | 0.9600 | 1600.0 | 11.71％ |
| Acrylic acid n-butyl ester | 128.17 | 338.37 | 2.6400 | 4400.0 | 28.65％ |
| Dimethyl sulfoxide | 78.13 | 355.2 | 30.08％ | ||
| Ethyl acetate | 88.11 | 128.1 | 10.85％ | ||
| Cupric bromide (II) | 223.37 | 0.001 | 0.0000 | 0.010 | 0.00％ |
| 2, 5-Dibromoadipic acid diethyl ester | 360.40 | 0.22 | 0.0006 | 1.00 | 0.02％ |
| Me-6TREN | 230.50 | 0.014 | 0.00006 | 0.100 | 0.00％ |
GPC scan for MW versus reaction time:
synthesis of a terpolymer of 2-ethylhexyl acrylate, n-butyl acrylate and 4-hydroxybutyl acrylate (NBJ 408534).
The synthesis procedure is described in the following feed ratios:
| MW | g | mole of | Molar ratio of | By weight% | |
| 2-ethylhexyl acrylate | 184.00 | 750.72 | 4.0800 | 6800.0 | 54.07％ |
| Acrylic acid 4-hydroxybutyl ester | 128.17 | 30.76 | 0.2400 | 400.0 | 2.22％ |
| Acrylic acid n-butyl ester | 128.17 | 61.52 | 0.4800 | 800.0 | 4.43％ |
| Dimethyl sulfoxide | 78.13 | 400.7 | 28.86％ | ||
| Acetic acid ethyl ester | 88.11 | 144.5 | 10.41％ | ||
| Cupric bromide (II) | 223.37 | 0.001 | 0.0000 | 0.010 | 0.00％ |
| 2, 5-Dibromoadipic acid diethyl ester | 360.40 | 0.22 | 0.0006 | 1.00 | 0.02％ |
| Me-6TREN | 230.50 | 0.014 | 0.00006 | 0.100 | 0.00％ |
GPC scanning vs. reaction time
Formulation testing
Modulus of elasticity
Optically Clear Adhesive (OCA) formulations having the following compositions were tested for modulus and creep recovery on an Anton Parr MCR 302 rheometer. To establish good contact with the rheometer plate, the initial liquid test sample was photocured at 100mW/cm2 UVA for 90 seconds to form a 600 micron film across the bottom quartz plate. Modulus measurements were typically made using 8-mm aluminum parallel plates and a liquid nitrogen cooling unit at-25 to 25 ℃ with 0.1% strain, 1Hz vibrational frequency, and zero normal force. A heating rate of 3 c/min was used initially and then switched to a heating rate of 5 c/min.
The modulus and Tg values of the formulations at-20 and 25 ℃ are given in tables 1 to 6. For consistent reporting and rapid data analysis, an auto-analysis macro (auto-analysis macro) was set up using the Anton Paar RheoPlus software to determine the modulus in megapascals (MPa), and Tg values at the temperatures of interest. In this study, the temperature corresponding to the peak maximum of tan (δ) was taken as Tg. If the tan (delta) peak is not completely captured within the temperature range studied, the Tg is considered to be below-25 ℃ and is reported in the following table as "< -25". Degree.C.
Creep recovery
After the above temperature sweep, the selected formulations were subjected to creep recovery testing by: the cured sample was strained to 200% in 0.2 seconds, allowed to relax at a constant strain of 200% for 20 minutes, and then monitored for strain recovery after all accumulated shear stress was immediately removed. The strain at 2400 seconds of test run was recorded and recovery was calculated using the following equation:
the 70D formulation described below showed significantly higher creep recovery of 98%. At the same time, the formulation has a modulus of 0.18MPa at-20 ℃ and a modulus of 0.02MPa at 25 ℃.
Temperature scan results
TABLE 1 run #1-10
TABLE 2 run #11-20
TABLE 3 run #21-30
TABLE 4 run #31-40
TABLE 5 run #41-50
TABLE 6 run #51-60
Applicants have surprisingly found that the incorporation of vinyl ether monomers into acrylate systems can significantly reduce the modulus and Tg of the resulting polymer while achieving high creep recovery at very low modulus. This combination of physical properties with very low modulus at low temperatures and very high creep recovery has never been observed before and is an unexpected result.
The formulations tested above had the following composition:
note: in the above table, "sum" means "sum", "mix" means "mixture", "dedocyl VE" means "dodecyl VE", "polycaprolactone" means "polycaprolactone" and "octylecyl" means "octyl decyl".
While the applicants have provided descriptions and examples of various embodiments of the present invention, the scope thereof is not limited to the specific embodiments, but is defined only in the appended claims. Those skilled in the art will appreciate that various modifications may be made to the embodiments of the disclosure without departing from the spirit and scope of the disclosure.
Claims (23)
1. A method of preparing an adhesive composition, the method comprising:
combining a urethane acrylate and a vinyl ether to form a mixture, and co-curing the mixture to form an adhesive composition, wherein the adhesive composition after curing has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃.
2. The method of claim 1, wherein the urethane acrylate is produced by:
providing a multi-branched diol; reacting the multi-branched diol with a diisocyanate to obtain a polyurethane; and reacting the polyurethane with an acrylate to form a polyurethane acrylate.
3. The method of claim 2, wherein the multi-branched diol is polyfarnesene or dimer acid polyester.
4. The method of claim 2, wherein the diol has a molecular weight greater than about 1000 g/mol.
5. The method of claim 1, wherein the co-curing is performed by photo-curing or thermal curing.
6. The method of claim 1, wherein the diisocyanate is an aliphatic diisocyanate.
7. The method of claim 1, wherein the urethane acrylate and vinyl ether are combined in a vinyl ether to urethane acrylate molar ratio of less than about 1.
8. The method of claim 1, wherein the urethane acrylate has a molecular weight of greater than about 25000 g/mol.
9. The method of claim 1 wherein the adhesive composition has a modulus of less than about 1.0mPa and a creep recovery of greater than about 70% at-20 ℃.
10. The method of claim 1 wherein the adhesive composition has a modulus of less than about 0.3mPa and a creep recovery of greater than about 90% at-20 ℃.
11. The method of claim 1, wherein the urethane acrylate has a glass transition temperature of less than 10 ℃.
12. The method of claim 1, wherein the urethane acrylate has a glass transition temperature of less than-30 ℃.
13. The method of claim 1, further comprising combining the urethane acrylate with a photoinitiator or thermal initiator prior to the co-curing step.
14. The method of claim 1, wherein the vinyl ether is a member selected from the group consisting of: poly (butyl vinyl ether), poly (ethyl vinyl ether), poly (hexyl vinyl ether), poly (isobutyl vinyl ether), poly (isopropyl vinyl ether), poly (methyl vinyl ether), poly (octyl vinyl ether), poly (propyl vinyl ether), and combinations thereof.
15. The method of claim 1, wherein the urethane acrylate is selected from the group consisting of poly (2-ethylhexyl acrylate), poly (2,2,3,3, -tetrafluoropropyl acrylate), poly (4-cyanobutyl acrylate), poly (butyl acrylate), poly (dodecyl acrylate), poly (ethyl acrylate), poly (hexyl acrylate), poly (isobutyl acrylate), poly (isopropyl acrylate), poly (nonyl acrylate), poly (propyl acrylate), poly (sec-butyl acrylate), poly (tetrahydrofurfuryl acrylate), poly (decyl methacrylate), poly (dodecyl methacrylate), poly (hexyl methacrylate), poly (isodecyl methacrylate), poly (octyl methacrylate), and combinations thereof.
16. An adhesive composition comprising a co-cured mixture of a urethane acrylate and a vinyl ether, wherein the adhesive composition has a modulus of less than about 10.0mPa and a creep recovery of greater than about 50% at-20 ℃.
17. The adhesive composition of claim 16 wherein the adhesive composition has a modulus of less than about 1.0mPa and a creep recovery of greater than about 70% at-20 ℃.
18. The adhesive composition of claim 16 wherein the adhesive composition has a modulus of less than about 0.3mPa and a creep recovery of greater than about 90% at-20 ℃.
19. The adhesive composition of claim 16, wherein the molar ratio of the vinyl ether to the acrylic monomer is equal to or less than about 1.
20. The adhesive composition of claim 16, wherein no solvent is present in the composition.
21. The adhesive composition of claim 16, wherein the composition further comprises a thermal initiator or a photoinitiator.
22. The adhesive composition of claim 16, wherein the vinyl ether is a member selected from the group consisting of: poly (butyl vinyl ether), poly (ethyl vinyl ether), poly (hexyl vinyl ether), poly (isobutyl vinyl ether), poly (isopropyl vinyl ether), poly (methyl vinyl ether), poly (octyl vinyl ether), poly (propyl vinyl ether), and combinations thereof.
23. The adhesive composition of claim 16, wherein the urethane acrylate is selected from the group consisting of poly (2-ethylhexyl acrylate), poly (2,2,3,3, -tetrafluoropropyl acrylate), poly (4-cyanobutyl acrylate), poly (butyl acrylate), poly (dodecyl acrylate), poly (ethyl acrylate), poly (hexyl acrylate), poly (isobutyl acrylate), poly (isopropyl acrylate), poly (nonyl acrylate), poly (propyl acrylate), poly (sec-butyl acrylate), poly (tetrahydrofurfuryl acrylate), poly (decyl methacrylate), poly (dodecyl methacrylate), poly (hexyl methacrylate), poly (isodecyl methacrylate), poly (octyl methacrylate), and combinations thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202062966221P | 2020-01-27 | 2020-01-27 | |
| US62/966,221 | 2020-01-27 | ||
| PCT/US2021/015085 WO2021154725A1 (en) | 2020-01-27 | 2021-01-26 | High creep recovery, low modulus polymer systems and methods of making them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115190905A true CN115190905A (en) | 2022-10-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180017469.4A Pending CN115190905A (en) | 2020-01-27 | 2021-01-26 | High creep recovery, low modulus polymer systems and methods of making the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20220380645A1 (en) |
| EP (1) | EP4097189A4 (en) |
| CN (1) | CN115190905A (en) |
| WO (1) | WO2021154725A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785862A (en) * | 2022-10-31 | 2023-03-14 | 苏州世华新材料科技股份有限公司 | Bio-based anti-warping acrylic pressure-sensitive adhesive and preparation method thereof |
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- 2021-01-26 EP EP21748173.8A patent/EP4097189A4/en active Pending
- 2021-01-26 CN CN202180017469.4A patent/CN115190905A/en active Pending
- 2021-01-26 WO PCT/US2021/015085 patent/WO2021154725A1/en unknown
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| US20160177149A1 (en) * | 2009-05-15 | 2016-06-23 | 3M Innovative Properties Company | Urethane-based pressure sensitive adhesives |
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| CN115785862B (en) * | 2022-10-31 | 2023-10-20 | 苏州世华新材料科技股份有限公司 | Bio-based anti-warping acrylic pressure-sensitive adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021154725A1 (en) | 2021-08-05 |
| US20220380645A1 (en) | 2022-12-01 |
| EP4097189A1 (en) | 2022-12-07 |
| EP4097189A4 (en) | 2024-02-21 |
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